FR2833606A1 - Diesel fuel compositions with reduced particulate emission, containing carbonate esters of glycerol acetal derivatives - Google Patents

Abstract

Diesel fuel composition containing carbonate(s) of glycerol acetal(s). Diesel fuel composition contains: (A) a major proportion of conventional diesel fuel(s); and (B) carbonate(s) of glycerol acetal(s) of formula (1) and/or (2). R1, R2 = H, 1-20C aliphatic, cycloaliphatic or aromatic hydrocarbyl, or an alkyl-ether chain, or R1 plus R2 may form an oxygen-containing heterocycle; R3 = same as R1/R2 (except H), or a group of formula (3) and/or (4).

Description

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 The invention relates to diesel fuel compositions containing oxygenated compounds consisting of glycerol acetal carbonates.

 Improving air quality is now a top priority for all major industrialized countries. Among the emitters of referenced pollutants, transport occupies a place that demands that important measures be taken to reduce its contribution. For example, regulatory packages have been in place for several years, with new constraints starting in 2000, including specifications on fuel quality. Indeed, in addition to the characteristics conventionally specified, new regulations on the chemical composition of fuels have emerged, with the aim of limiting the precursors of certain pollutants, such as particles, the compounds that are reactive with respect to tropospheric ozone or toxic compounds. In this context, it is clear that all steps to improve the quality of products to propose mixtures significantly reducing pollutant releases are promising.

 It is one of the objects of the invention to propose the use of glycerol acetal carbonates as additives or as bases for the formulation of gas oils, leading to significant reductions in particle emissions.

HzC-O Ri CH2-0 Ri i HC-O R2 et/ou R3-o-C-O-CH 1 Il \ l'R HC-O-C-O-Rs 0 CH2-0 2 il 0 (1) (2) où :
RI et R2 représentent chacun un atome d'hydrogène, un radical hydrocarboné de
1 à 20 atomes de carbone, aliphatique, linéaire ou ramifié, saturé ou non, cycloaliphatique ou aromatique, ou une chaîne alkyl-éther, RI et R2 pouvant former ensemble un radical hétérocyclique oxygéné (par exemple furanique ou tétrahydrofuranique) ; - R3 est un radical défini comme RI ou R2, sauf l'atome d'hydrogène, ou un radical de formule générale : The glycerol acetal carbonates considered in the invention correspond to one of the following general formulas:

Wherein R 1 and R 3 -OCO-CH 1 R 2 O -CH 2 O-CH 2 O 2 O (1) (2) where:
R1 and R2 each represent a hydrogen atom, a hydrocarbon radical of
1 to 20 carbon atoms, aliphatic, linear or branched, saturated or unsaturated, cycloaliphatic or aromatic, or an alkyl-ether chain, R1 and R2 may together form an oxygenated heterocyclic radical (for example furanic or tetrahydrofuranic); - R3 is a radical defined as RI or R2, except the hydrogen atom, or a radical of general formula:

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H2C-0 c (RI CH2-Q RI hic HC-Cr R \/\ H--

où RI et R2 sont définis comme ci-dessus.

H2C-0 c (RI CH2-Q RI HC HC-Cr R \ / \ H--

where R1 and R2 are defined as above.

Most often, R 1 and R 2 are each a hydrogen atom, a methyl, ethyl or propyl radical and R 3 is a methyl or ethyl radical.

H2C-0 RI CH2-0 RI Ht-CY"C : : R2 et/ou H0-CíÍ \ ! et/ou HO-C \é CH2-0 2

A partir de ces produits, on réalise l'introduction d'une fonction carbonate par exemple par réaction de trans-carbonatation selon le schéma :

H2C-0 Ri CH2-0 Ri 1 HC-0-R2 HO-CH d HC-e 'Rz HC-OH -0

The products considered in the invention are generally obtained from glycerol acetals of general structure:

H2C-O R1 CH2-O-R1H2-CY "C: R2 and / or H0-C11 and / or HO-C # CH2-O2

From these products, the introduction of a carbonate function is carried out for example by trans-carbonation reaction according to the scheme:

H2C-O R1 CH2-O1 Ri1 HC-O-R2 HO-CHd HC-e 'Rz HC-OH -0

H2C-0 Ri CH2-0 Ri et/ou/"ci HC-O R2 ou R3- -C-0-CH d H2C-o-C-o-R3 0 CH2-O 0 0 il u

où RI, R2 et R3 sont définis comme précédemment, R3 étant le plus souvent un radical méthyle ou éthyle.

H2C-O R1 CH2-O1 R1 and / or C1-C3 R2 or R3-C-O-CH d H2C-OCo-R3 O CH2-O 0 0 u

where R1, R2 and R3 are defined as above, R3 being most often a methyl or ethyl radical.

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 This reaction is generally carried out in a basic medium with a catalyst selected for example from hydroxides, carbonates, alkoxides and hydrides of alkali or alkaline earth metals or other metals.

 This reaction can also be carried out by condensation of a urethane of general formula R 3 -CO-NH 2 on the free hydroxyl function of the glycerol acetals with release of ammonia, the urethane R 3 -CO-NH 2 which can itself be obtained easily by condensation of the alcohol R3-OH with urea.

 Other reactions may be envisaged to introduce a carbonate function.

They are listed in an article that reviews it using dimethyl carbonate as an example: Rewiew of Dimethyl Carbonate Manufacture and its Characteristics as a Fuel Additive in Energy & Fuels, vol. 11, pp. 2-29 (1997).

The glycerol acetals are themselves prepared most often by reaction, usually in an acid medium of an aldehyde or a ketone on glycerol or by transacetalization reaction. These reactions, applied to an R-OH alcohol, are represented by the diagrams below: 2R-OH + R'CHO (RO) 2CH-R '+ H 2 O (3)
2 R-OH + (R "O) 2 CH-R '-7 (RO) 2 CH-R' + 2 R" OH (4)
When applied to glycerol, acetalization or transacetalization reactions are numerous. Some can be written according to the following diagrams:

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0 Ir OR3 if Il RjC- R2 (-H20) Rj6-R2 (-R30H) ORg (avec R3 différent de H) \ 1. J 1 Ri -ORi i H-ORz HO-CH H. C-OH CH.-d H2C-OH

## STR1 ## wherein R 1 is R 2 (-H 2 O) R 6 -R 2 (-R 3 OH) OR 6 (with R 3 other than H). ## STR1 ## d H2C-OH

H2C-0 Ri CH2-0 R) 1 Ho-if R SCH C et/ou \, \/\ 1712L-O R, ( : \H2 H2C-O RI "é R40 R2 RI "OR4

Ces réactions appliquées au glycérol sont décrites par exemple dans les publications suivantes : - Piantadosi et coll, J. of Am. Chem. Soc, (1958), 6613 - Gelas et coll, Bull Soc Chim Fr, (1969), n 4, 1300 ibid., (1970), n 6, 2341 ibid., (1970), n 6, 2349 - Gelas et coll, CR. Ac. Sc. Paris (1970), 218.

H2C-O R 1 CH 2 -O R) 1 Ho-if R SCH C and / or 1, R 1, R 2, R 2, R 2, OR 4

These reactions applied to glycerol are described, for example, in the following publications: Piantadosi et al., J. of Am. Chem. Soc., (1958), 6613 - Gelas et al, Bull Soc Chim Fr, (1969), No. 4, 1300 ibid., (1970), No. 6, 2341 ibid., (1970), No. 6, 2349 - Gelas et al. coll, CR. Ac. Sc. Paris (1970), 218.

The products used in the invention may consist of one or more compounds corresponding to the general formulas (1) and (2).

The introduction of these products into the diesel engine fuel compositions leads to diesel fuels allowing a reduction in

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 pollutant emissions, including particulate emissions in relation to fuel not containing the products in question.

 In the diesel fuel compositions according to the invention, the diesel fuel in question may be of petroleum origin or a mixture of alkyl esters derived from vegetable oils.

 According to the invention, the diesel fuel compositions of the invention may contain glycerol acetals in various proportions. The glycerol acetal carbonate or each of the glycerol acetal carbonates will be introduced into the diesel fuel at a concentration such that it is soluble in said diesel fuel. Depending on the case, proportions of 1 to 40% by volume, usually 1 to 20% by volume, are used.

 The following examples illustrate the invention without limiting it.

EXAMPLES
In Examples 1 and 2, the synthesis of glycerol acetal carbonates is described.

Example 3 describes tests for evaluating the performance of gas oil compositions closing the glycerol acetal carbonates prepared in Examples 1 and 2.

Example 1
920 g (10 moles) of glycerol, 790.3 g (10.96 moles) of n-butyraldehyde and 24 g of an acidic Amberlyst® resin are introduced into a reactor. The mixture is brought to 54 ° C. with stirring for 7 hours, during which time 120 g of n-butyraldehyde are introduced.

After returning to ambient temperature, the catalyst is removed by filtration, and the excess n-butyraldehyde and the reaction water are removed by evaporation under reduced pressure. 1165 g of a clear liquid soluble in diesel fuel are collected and the elementary analysis of which is as follows:
C = 56.7% mass
H = 10.1% mass
0 = 33.2% mass and which corresponds mainly to the following formula:

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H2C-Q CH2-0 z CHCH2CH2CH3 et/ou HO-CH CHCH2CH2CH3 Hc-if \/ 1 CH2-0 H2C-OH

Dans un réacteur équipé d'un séparateur de Dean & Stark, on introduit 400 g de ce produit, 970 g (8,2 mole) de carbonate de diéthyle, puis 4 g d'hydrure de sodium. On porte le milieu à 80 C, puis progressivement à 140 C tout en éliminant l'éthanol de réaction formé au moyen du séparateur de Dean & Stark. Après 5 heures de réaction, et retour du milieu à la température ambiante, on procède à la neutralisation du catalyseur avec par exemple une quantité suffisante d'acide chlorhydrique dilué dans de l'alcool, puis après filtration on évapore les solvants et les réactifs en excès sous pression réduite. On obtient 532 g d'un liquide limpide soluble dans le gazole et dont l'analyse élémentaire est la suivante :
C = 55,35 % masse
H = 8,25 % masse
0 = 36,4 % masse

et qui correspond majoritairement à la formule suivante :

H2C-O, CH2-0 I 1/CHCH2CH2CH3 et/ou CH3CH2-C03-CH CHCH2CH2CH3 HC-O'-' 1 CH2-Q H2C-C03-CH2CH3

On répète l'opération complète illustrée par cet exemple de manière à disposer de 1 litre de produit.

H2C-Q CH2-0 z CHCH2CH2CH3 and / or HO-CHCHCH2CH2CH3 Hc-if / CH2-0H2C-OH

In a reactor equipped with a Dean & Stark separator, 400 g of this product, 970 g (8.2 mol) of diethyl carbonate and 4 g of sodium hydride are introduced. The medium is brought to 80 ° C. and then gradually to 140 ° C. while eliminating the reaction ethanol formed using the Dean & Stark separator. After 5 hours of reaction, and returning to the medium at room temperature, the catalyst is neutralized with, for example, a sufficient amount of hydrochloric acid diluted in alcohol, and after filtration, the solvents and the reagents are evaporated. excess under reduced pressure. 532 g of a clear liquid which is soluble in diesel fuel and whose elemental analysis is as follows:
C = 55.35% mass
H = 8.25% mass
0 = 36.4% mass

and which corresponds mainly to the following formula:

H2C-O, CH2-O1 1 / CHCH2CH2CH3 and / or CH3CH2-CO3-CH CHCH2CH2CH3 HC-O1-CH2-Q H2C-CO3-CH2CH3

The complete operation illustrated by this example is repeated so as to have 1 liter of product.

Example 2
Example 1 is repeated replacing n-butyraldehyde with an equimolar amount of acetone. The product of the reaction corresponds mainly to the following formula:

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et qui correspond majoritairement à la formule suivante :

H2C-O., c (CH3 CH2-0 CH3 HC-OCHs et/ou CH3CH2-0-C-0-CH il H2C-0-C-0-CH2CH3 ) (H2-C 3 0 0
On répète l'opération complète illustrée par cet exemple de manière à disposer de 1 litre de produit. In a reactor equipped with a Dean & Stark separator, 132 g of this product are charged with 590 g (5 moles) of diethyl carbonate and then with sodium hydride Ig. The medium is brought to 80 ° C. and then gradually to 140 ° C. while eliminating the reaction ethanol formed using the Dean & Stark separator. After 5 hours of reaction and return of the medium to room temperature, the catalyst is neutralized with, for example, a sufficient amount of hydrochloric acid diluted in alcohol, then after filtration, the solvents and the excess reagents are evaporated off. under reduced pressure. We obtain 190 g of a clear liquid soluble in diesel fuel and whose elemental analysis is as follows:
C = 52. 4% mass
H = 7.8% mass
0 = 39.8% mass

and which corresponds mainly to the following formula:

H2C-O., C (CH3 CH2-CH3 HC-OCHs and / or CH3CH2-O-C-O-CH1H2C-O-C-O-CH2CH3) (H2-C30)
The complete operation illustrated by this example is repeated so as to have 1 liter of product.

Example 3
Attempts were made to evaluate the performance of the gas oil compositions closing the glycerol acetals prepared in the preceding examples.

obtenues avec le gazole seul. t : l
Les essais ont été effectués à partir d'un gazole représentatif des formulations Euro 2000 : densité de l'ordre de 0,832 à 15 C, teneur en soufre de l'ordre de 300 ppm, indice de cétane de l'ordre de 53, intervalle de distillation 170/366 C. The particulate emissions measured with these fuels will be compared to those

obtained with diesel alone. t: l
The tests were carried out using a gas oil representative of the Euro 2000 formulations: density in the range of 0.832 to 15 ° C., sulfur content of the order of 300 ppm, cetane number of about 53, range Distillation 170/366 C.

 The tests were conducted on a diesel vehicle equipped with a direct injection engine.

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 These tests were carried out on the cycle imposed by the European directive 70/220 / EC, modified by the directive 98/69 / EC (called cycle MVEG-lls Euro 2000). This cycle consists of an urban phase (ECE cycle with a length of 4,052 km) and an extra-urban phase (6,955 km cycle EUDC). The test results, expressed in gram of particles per kilometer, are presented on each phase of the cycle and on the complete cycle.

 The results obtained are collated in the following Table 1. They are expressed in gram of particles emitted per kilometer (g / km).

Table 1

<Tb>
<tb> Emission <SEP> of <SEP> particles <SEP> (g / km)
<tb> Fuel <SEP> Assessed <SEP> Cycle <SEP> ECE <SEP> Cycle <SEP> EUDC <SEP> Cycle <SEP> MVEG
<tb> Gas oil <SEP> alone <SEP> 0.0635 <SEP> 0.0517 <SEP> 0.0560
<tb> Gas oil <SEP>: <SEP> 95% <SEP> volume <SEP> + <SEP> 0.0449 <SEP> 0.0374 <SEP> 0.0420
<tb> Product <SEP> of <SEP> Example <SEP> 1 <SEP>: <SEP> 5% <SEP> volume
<tb> Gas oil <SEP>: <SEP> 95% <SEP> volume <SEP> + <SEP> 0.0556 <SEP> 0.0455 <SEP> 0.0492
<tb> Product <SEP> of <SEP> Example <SEP> 2 <SEP>: <SEP> 5% <SEP> volume
<Tb>

The reductions of particulate emissions with the fuels according to the invention vary from 12% to 29% over all the conditions tested in this example.

Claims (6)

R 1 and R 2 each represent a hydrogen atom, a hydrocarbon radical of ## STR2 ## or R 3 -O-C-O-CH 2 0 CH2- (/ 2 il 0 (1) (2) wherein: glycerol corresponding to one of the general formulas: 1. Diesel fuel composition characterized in that it comprises a major proportion of at least one diesel fuel conventional and at least one acetal carbonate of 1 to 20 carbon atoms, aliphatic, cycloaliphatic or aromatic, or an alkyl-ether chain, R1 and R2 may together form an oxygenated heterocyclic radical; - R3 is a radical defined as RI or R2, except the hydrogen atom, or a radical of general formula:

 H2C-O R1 Cj12-R1Hy ryT? and / or CH 2 CH 2 -O 2 where R 1 and R 2 are as defined above.  glycerol acetal carbonate formula, R1 and R2 are each a hydrogen atom, ZD a methyl, ethyl or propyl radical and R3 is a methyl or ethyl radical.

2. Diesel fuel composition according to claim 1 characterized in that, in the 3. Diesel fuel composition according to claim 1 or 2, characterized in that it comprises a conventional diesel fuel and a proportion of 1 to 40% by volume of at least one glycerol acetal carbonate defined as in claim 1. . 4. Diesel fuel composition according to claim 3 characterized in that the proportion of glycerol acetal carbonate is 1 to 20% by volume. <Desc / Clms Page number 10>  5. diesel fuel composition according to one of claims 1 to 4 characterized in that said conventional diesel fuel is a diesel fuel of petroleum origin. 6. Diesel fuel composition according to one of claims 1 to 4 characterized in that said conventional diesel fuel is a mixture of alkyl esters derived from vegetable oils.